CN109772439B - Tert-butyl alcohol refining catalyst and preparation method and application thereof - Google Patents

Tert-butyl alcohol refining catalyst and preparation method and application thereof Download PDF

Info

Publication number
CN109772439B
CN109772439B CN201711119008.XA CN201711119008A CN109772439B CN 109772439 B CN109772439 B CN 109772439B CN 201711119008 A CN201711119008 A CN 201711119008A CN 109772439 B CN109772439 B CN 109772439B
Authority
CN
China
Prior art keywords
catalyst
acid
solution
hours
hzsm
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201711119008.XA
Other languages
Chinese (zh)
Other versions
CN109772439A (en
Inventor
张信伟
徐会青
李�杰
王海洋
尹泽群
刘全杰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
Original Assignee
China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Dalian Research Institute of Petroleum and Petrochemicals filed Critical China Petroleum and Chemical Corp
Priority to CN201711119008.XA priority Critical patent/CN109772439B/en
Publication of CN109772439A publication Critical patent/CN109772439A/en
Application granted granted Critical
Publication of CN109772439B publication Critical patent/CN109772439B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Landscapes

  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a tertiary butanol refining catalyst, a preparation method and application thereof. The total content of the Silicate-1 and the HZSM-5 is 0.1-10% by weight of the catalyst; with P2O5The content of the P element is 0.01-10%; the content of the VIII group noble metal is 0.01-10%; the balance of inorganic refractory oxide, wherein the weight ratio of the Silicate-1 to the HZSM-5 is 1: 0.1-10; the preparation method of the refined catalyst comprises the following steps: the in-situ synthesis method is adopted to prepare the catalyst containing Silicate-1, HZSM-5 and P2O5A composite carrier of an inorganic refractory oxide; then loading the VIII group noble metal on the carrier to prepare the catalyst. The catalyst has excellent removal capacity for organic peroxide, organic acid ester and other impurities in the tert-butyl alcohol raw material, and the removal rate of the impurities reaches more than 99%.

Description

Tert-butyl alcohol refining catalyst and preparation method and application thereof
Technical Field
The invention relates to a tert-butyl alcohol (TBA) refined catalyst, a preparation method and application thereof.
Background
Propylene oxide is the third largest propylene derivative besides polypropylene and acrylonitrile, and is an important basic organic chemical raw material. The method is mainly used for producing polyether polyol, nonionic surfactant, propylene carbonate and propylene glycol, is an important raw material of fine chemical products, and is widely applied to industries such as automobiles, buildings, food, tobacco, medicine, cosmetics and the like.
The existing propylene oxide production technology mainly comprises the following steps: chlorohydrin process, co-oxidation process, direct oxidation process. The environmental disadvantages of the chlorohydrin process have led to the gradual market withdrawal of this route. The new project mainly considers the co-oxidation method and the direct oxidation method. The co-oxidation process comprises: ethylbenzene co-oxidation (PO/SM), isobutane co-oxidation (PO/TBA, PO/MTBE), cumene oxidation (CHP). The domestic Zhonghai shell 25 million t/a PO device and the Zhongpetrochemical Zhehai 28.5 million t/a PO device adopt the PO/SM method technology. Two sets of devices are built by New Material Ltd of Steed Wanhua and Nanjing Jinling Hunst, the PO/MTBE proprietary technology of Hunst is adopted, and the scales are both 24 ten thousand/a PO and 75 ten thousand/a MTBE.
The PO/MTBE combination comprises: the method comprises the unit processes of iso-butane oxidation, propylene epoxidation, product separation and purification, Tertiary Butyl Alcohol (TBA) refining, MTBE synthesis and the like. Among them, the TBA material after epoxidation contains impurities such as organic acid esters, peroxides, etc., which may adversely affect the subsequent synthesis of MTBE. Therefore, before entering the MTBE synthesis unit, the TBA is purified to remove impurities. However, domestic studies on purification of TBA are still blank.
The development of TBA refining technology is an important matching content in PO/MTBE technology, develops technology with independent intellectual property rights, is favorable for accelerating the development progress of PO/MTBE technology in China, masters the core technology of key steps and breaks through foreign technical blockade.
The TBA feedstock from the PO/MTBE complex contains a variety of impurities, including organic acid ester impurities: tert-butyl formate (TBF), isobutyl formate (IBF), organic peroxide impurities including: t-butyl hydroperoxide (TBHP), di-t-butyl peroxide (DTBP). These four impurities have negative effects on downstream processes and therefore must be treated to remove the impurities before entering the downstream processes.
Disclosure of Invention
The invention provides a tertiary butanol refining catalyst and a preparation method thereof according to the property difference of TBF, IBF, TBHP and DTBP in TBA raw materials. The catalyst integrates three functions of cracking, adsorption and hydrogenation, has excellent removal capability on impurities such as organic peroxides (TBHP, DTBP), organic acid esters (TBF, IBF) and the like in TBA raw materials, and has the impurity removal rate of more than 99%.
A tertiary butanol refining catalyst, the total content of Silicate-1 and HZSM-5 is 0.1-10%, preferably 0.1-1% by weight of the catalyst; with P2O5The content of the P element is 0.01-10%, preferably 0.5-5%; VII thThe content of the I group noble metal is 0.01-10%, preferably 0.05-1%; wherein the weight ratio of the Silicate-1 to the HZSM-5 is 1: 0.1-10, preferably 1: 0.1-1.
A tertiary butanol refining catalyst, wherein the aperture of the catalyst is 2-50 nm, preferably 5-11 nm; the acid amount of the catalyst at 250-350 ℃ is 0.1-2.1 mmol/g; preferably 0.5 to 0.9 mmol/g.
In the catalyst, the VIII group noble metal is one or more of Pt and Pd, and preferably Pt.
In the catalyst, the catalyst contains an inorganic refractory oxide, wherein the inorganic refractory oxide is one or more of alumina, silica, titania, magnesia and zirconia, preferably one or more of alumina and silica, and more preferably alumina.
A preparation method of a tertiary butanol refining catalyst comprises the following steps: the in-situ synthesis method is adopted to prepare the catalyst containing Silicate-1, HZSM-5 and P2O5A composite carrier of an inorganic refractory oxide; then loading the VIII group noble metal on the carrier to prepare the catalyst of the invention.
A preparation method of a tertiary butanol refining catalyst specifically comprises the following steps:
(1) adding a template agent, an organic acid and an inorganic acid into a tert-butyl alcohol-water binary solvent according to a certain proportion, and adjusting the pH value of the solution to 1-3; adding aluminum isopropoxide, Silicate-1 and HZSM-5 into the solution, and stirring for 1-6 hours at 50-70 ℃; then crystallizing the solution;
(2) after crystallization is finished, filtering and drying the crystallized product, uniformly mixing the crystallized product with a peptizing agent and an extrusion aid, kneading and molding, and drying and roasting to obtain a composite carrier;
(3) and (3) loading the VIII group noble metal on the carrier obtained in the step (2), and drying and roasting to obtain the tertiary butanol refining catalyst.
In the step (1), the template is a mesoporous template, preferably one or more of P123 and fatty alcohol-polyoxyethylene ether, and more preferably P123.
In the step (1), the organic acid is one or more of citric acid and tartaric acid, and preferably citric acid.
In the step (1), the inorganic acid is one or more of phosphoric acid and boric acid, and is preferably phosphoric acid.
In the step (1), the molar ratio of the template agent, the organic acid, the inorganic acid and the tertiary butanol is (0.01-1): 1-20): 100, preferably (0.05-0.1): 1-5): 5-10): 100.
In the step (1), the mass fraction of the tertiary butanol in the tertiary butanol-water binary solvent is 3.9-93.6%, preferably 69.4-87.5%.
In the step (1), the mass fraction of the aluminum isopropoxide in the solution is 5-30%, preferably 8-15%.
In the step (1), the mass fraction of the Silicate-1 in the solution is 0.001-0.1%, preferably 0.005-0.02%.
In the step (1), the mass fraction of the HZSM-5 in the solution is 0.001-0.1%, preferably 0.001-0.05%.
In the step (1), the crystallization temperature is 80-200 ℃, and preferably 100-150 ℃; the crystallization time is 8 to 48 hours, preferably 12 to 24 hours.
In the step (2), the peptizing agent is nitric acid, hydrochloric acid, acetic acid, citric acid and the like, preferably nitric acid. The mass concentration of the nitric acid solution is 1-25%, and preferably 1-6%. The amount of the nitric acid solution is based on the amount of the kneaded mass which can be formed into a plastic mass.
In the step (2), the extrusion aid is a substance which is beneficial to extrusion molding, such as one or more of graphite, starch, cellulose and sesbania powder, and preferably sesbania powder. The mass fraction of the extrusion aid in the forming body is 1-20%, and preferably 2-8%.
In the step (2), the drying temperature is 80-200 ℃, and preferably 100-120 ℃; the drying is carried out for 6 to 48 hours, preferably for 8 to 12 hours.
In the step (2), the roasting temperature is 300-900 ℃, and preferably 500-700 ℃; the roasting time is 2-24 hours, preferably 4-8 hours.
In the step (3), the loading mode of the VIII group noble metal is an impregnation method.
In the step (3), the impregnation solution is a water-soluble compound solution containing a group VIII noble metal.
In the step (3), the VIII group noble metal is one or more of Pt and Pd, and preferably Pt.
In the step (3), the Pt-containing compound is a chloroplatinic acid and platinum ammonium complex, preferably chloroplatinic acid.
In the step (3), the solid-liquid mass ratio of the impregnation liquid to the modified carrier is (0.5-2): 1, preferably (0.8-1.2): 1.
In the step (3), the drying temperature is 80-200 ℃, and preferably 100-120 ℃; the drying is carried out for 6 to 48 hours, preferably for 8 to 12 hours.
In the step (3), the roasting temperature is 300-800 ℃, and preferably 400-600 ℃; the roasting time is 2-24 hours, preferably 4-8 hours.
The catalyst is used for refining tertiary butanol, and the reaction conditions are as follows: adopting a fixed bed reactor, wherein the volume ratio of the tert-butyl alcohol raw material to the hydrogen is (10-100): 1, preferably (20-40): 1; the feeding volume airspeed is 0.5-3.0 h-1Preferably 1.5 to 2.5 hours-1(ii) a The reaction temperature is 150-300 ℃, and preferably 170-210 ℃; the reaction pressure is 0.5 to 5MPa, preferably 1.5 to 3 MPa.
Before the catalyst is used, reduction treatment needs to be carried out in advance in a hydrogen atmosphere, wherein the reduction temperature is 200-600 ℃, and preferably 300-400 ℃; the reduction time is 2 to 12 hours, preferably 2 to 6 hours.
The tertiary butanol refining catalyst and the preparation method thereof provided by the invention have the beneficial effects that:
1. the catalyst provided by the invention has the functions of removing organic peroxides (TBHP, DTBP) and organic acid esters (TBF and IBF), has excellent performance in tertiary butanol refining, has the removal rate of the organic peroxides and the organic acid esters of more than 99 percent, and can completely meet the requirements of downstream processes;
2. the invention can crack organic peroxides such as TBHP, DTBP and the like by regulating and controlling the acidity of the catalyst to form a cracking center, thereby realizing the purpose of high-efficiency removal;
3. the Silicate-1 and HZSM-5 components in the catalyst endow the catalyst with a function of selectively adsorbing organic acid ester, and the organic acid ester in the raw material can be adsorbed on the catalyst; then under the hydrogenation of noble metal, converting organic acid ester into corresponding alcohol;
4. in the preparation process of the catalyst provided by the invention, tert-butyl alcohol is used as a pore-enlarging agent, and a proper pore structure is formed on the catalyst, so that tert-butyl alcohol molecules can be conveniently diffused in the catalyst, and the deep hydrogenation reaction of tert-butyl alcohol can be avoided.
Detailed Description
The technical contents and effects of the present invention will be further described with reference to examples, but the present invention is not limited thereto. The chromatographic analysis conditions of the tert-butyl alcohol raw material and the product are as follows: an Agilent 7890A gas chromatograph, a FID detector and a DB-1301 chromatographic column, and an internal standard method is adopted for quantitative analysis, wherein the internal standard substance is benzyl alcohol. The calculation method of the impurity removal rate comprises the following steps:
Figure 219067DEST_PATH_IMAGE001
example 1
Adding P123, citric acid and phosphoric acid into a binary solvent containing 87.3wt% of tert-butyl alcohol and 12.7wt% of water at a molar ratio of P123: citric acid: phosphoric acid: tert-butyl alcohol of 0.07: 3.6: 7.2: 100, and stirring at room temperature to dissolve; weighing aluminum isopropoxide, Silicate-1 and HZSM-5, adding the aluminum isopropoxide, the Silicate-1 and the HZSM-5 into the solution according to the use amounts of 11.5wt%, 0.016wt% and 0.008wt% of the total mass of the solution, and stirring for 1 hour at 70 ℃; then pouring the solution into an autoclave lined with polytetrafluoroethylene for crystallization for 16 hours at 125 ℃; the crystallized product is filtered, washed and dried at 120 ℃ for 12 hours. The obtained material is crushed to be below 300 meshes, is uniformly mixed with 3wt% of sesbania powder, is kneaded by a nitric acid (with the concentration of 4.5 wt%) solution accounting for 75wt% of the total mass of the powder, is extruded into a plastic paste strip, is dried at 120 ℃ for 12 hours, and is roasted at 700 ℃ for 6 hours to obtain the composite carrier. Mixing the carrier and the chloroplatinic acid solution according to the solid-to-liquid ratio of 1: 1, soaking at room temperature for 12 hours, drying at 120 ℃ for 12 hours, and roasting at 550 ℃ for 4 hours to obtain the catalyst A1.
The catalyst evaluation is carried out in a fixed bed continuous micro flow reactor, the catalyst is reduced for 4 hours at 350 ℃ in the hydrogen atmosphere in advance, after the reduction is finished, the temperature of the reactor is reduced to a set value, and the raw material is introduced for carrying out the tertiary butanol refining reaction. The reaction conditions are as follows: the volume ratio of the tert-butyl alcohol raw material to the hydrogen is 30: 1; the space velocity of the feeding volume is 2.5 h-1(ii) a The reaction temperature is 190 ℃; the reaction pressure was 2.0 MPa.
The catalyst composition is shown in Table 1, and the reaction results are shown in Table 2.
Example 2
Catalyst preparation and evaluation the same as example 1 except that: the molar ratio of P123: citric acid: phosphoric acid: tert-butyl alcohol is 0.05: 4.5: 9.5: 100; the binary solvent comprises the following components: tert-butyl alcohol 75.6wt% -water 24.4 wt%.
The catalyst composition is shown in Table 1, and the reaction results are shown in Table 2.
Example 3
Catalyst preparation and evaluation the same as example 1 except that: the molar ratio of P123: citric acid: phosphoric acid: tert-butyl alcohol is 0.08: 2.5: 8.0: 100; the binary solvent comprises the following components: tert-butyl alcohol 72.4wt% -water 27.6 wt%.
The catalyst composition is shown in Table 1, and the reaction results are shown in Table 2.
Example 4
Catalyst preparation and evaluation the same as example 1 except that: the molar ratio of P123: citric acid: phosphoric acid: tert-butyl alcohol is 0.09: 1.5: 6.5: 100; the binary solvent comprises the following components: tertiary butanol 64.4wt% and water 35.6 wt%.
The catalyst composition is shown in Table 1, and the reaction results are shown in Table 2.
Example 5
Catalyst preparation and evaluation the same as example 1 except that: the mass fractions of aluminum isopropoxide, Silicate-1 and HZSM-5 in the solution are 15wt%, 0.02wt% and 0.001 wt%; the crystallization temperature is 140 ℃, and the crystallization time is 10 hours; the roasting temperature of the carrier is 600 ℃, and the roasting time is 8 hours.
The catalyst composition is shown in Table 1, and the reaction results are shown in Table 2.
Example 6
Catalyst preparation and evaluation the same as example 1 except that: the mass fractions of aluminum isopropoxide, Silicate-1 and HZSM-5 in the solution are 13wt%, 0.01wt% and 0.02 wt%; the crystallization temperature is 115 ℃, and the crystallization time is 20 hours; the roasting temperature of the carrier is 650 ℃, and the roasting time is 7 hours.
The catalyst composition is shown in Table 1, and the reaction results are shown in Table 2.
Example 7
Catalyst preparation and evaluation the same as example 1 except that: the mass fractions of aluminum isopropoxide, Silicate-1 and HZSM-5 in the solution are 9wt%, 0.005wt% and 0.04 wt%; the crystallization temperature is 100 ℃, and the crystallization time is 24 hours; the calcination temperature of the carrier was 550 ℃ and the calcination time was 7.5 hours.
The catalyst composition is shown in Table 1, and the reaction results are shown in Table 2.
Example 8
Catalyst preparation and evaluation the same as example 1 except that: the Pt content in the catalyst is 0.55 wt%; the roasting temperature of the catalyst is 500 ℃, and the roasting time is 8 hours.
The catalyst composition is shown in Table 1, and the reaction results are shown in Table 2.
Example 9
Catalyst preparation and evaluation the same as example 1 except that: the Pt content in the catalyst is 0.25 wt%; the roasting temperature of the catalyst is 600 ℃, and the roasting time is 6 hours.
The catalyst composition is shown in Table 1, and the reaction results are shown in Table 2.
Example 10
Catalyst preparation and evaluation the same as example 1 except that: the Pt content in the catalyst is 0.15 wt%; the roasting temperature of the catalyst is 450 ℃, and the roasting time is 7 hours.
The catalyst composition is shown in Table 1, and the reaction results are shown in Table 2.
Example 11
Catalyst A1 was prepared as in example 1. The catalyst evaluation was the same as in example 1, except that: the reaction temperature was 170 deg.C, 180 deg.C, 200 deg.C, 210 deg.C, respectively.
The reaction results are shown in Table 2.
Example 12
Catalyst A1 was prepared as in example 1. The catalyst evaluation was the same as in example 1, except that: the reaction pressures were 1.5MPa, 2.5MPa, and 3.0MPa, respectively.
The reaction results are shown in Table 2.
Example 13
Catalyst A1 was prepared as in example 1. The catalyst evaluation was the same as in example 1, except that: the space velocity of the feeding volume is 1.5 h respectively-1、2.0 h-1、3.0 h-1。
The reaction results are shown in Table 2.
Example 14
Catalyst A1 was prepared as in example 1. The catalyst evaluation was the same as in example 1, except that: the volume ratio of the tert-butyl alcohol raw material to the hydrogen is 20: 1 and 40: 1 respectively.
The reaction results are shown in Table 2.
Example 15
Catalyst A1 was prepared as in example 1. The catalyst evaluation was the same as in example 1, except that: the reduction temperatures of the catalysts were 300 ℃ and 400 ℃ respectively.
The reaction results are shown in Table 2.
Comparative example 1
Catalyst preparation and evaluation the same as example 1 except that: phosphoric acid, Silicate-1 and HZSM-5 are not added, and pure water is only used as a solvent and tert-butyl alcohol is not added in the preparation process of the carrier. Reference B1 was made.
The composition of reference B1 is shown in Table 1, and the reaction results are shown in Table 2.
Comparative example 2
Catalyst preparation and evaluation the same as example 1 except that: phosphoric acid was not added. Reference B2 was made.
The composition of reference B2 is shown in Table 1, and the reaction results are shown in Table 2.
Comparative example 3
Catalyst preparation and evaluation the same as example 1 except that: without Silicate-1 and without HZSM-5. Reference B3 was made.
The composition of reference B3 is shown in Table 1, and the reaction results are shown in Table 2.
Comparative example 4
Catalyst preparation and evaluation the same as example 1 except that: HZSM-5 was not added. Reference B4 was made.
The composition of reference B4 is shown in Table 1, and the reaction results are shown in Table 2.
Comparative example 5
Catalyst preparation and evaluation the same as example 1 except that: in the preparation process of the carrier, pure water is only used as a solvent, and tert-butyl alcohol is not added. Reference B5 was made.
The composition of reference B5 is shown in Table 1, and the reaction results are shown in Table 2.
TABLE 1
Figure 887946DEST_PATH_IMAGE002
TABLE 2
Figure 818993DEST_PATH_IMAGE004

Claims (11)

1. A tertiary butanol refining catalyst, characterized in that: the total content of the Silicate-1 and the HZSM-5 is 0.1-10% by weight of the catalyst; with P2O5The content of the P element is 0.01-10%; the content of the VIII group noble metal is 0.01-10%; wherein the weight ratio of the Silicate-1 to the HZSM-5 is 1: 0.1-10;
the aperture of the catalyst is 2-50 nm; the acid amount of the catalyst at 250-350 ℃ is 0.1-2.1 mmol/g;
the preparation method of the catalyst specifically comprises the following steps: (1) adding a template agent, an organic acid and an inorganic acid into a tert-butyl alcohol-water binary solvent according to a certain proportion, and adjusting the pH value of the solution to 1-3; adding aluminum isopropoxide, Silicate-1 and HZSM-5 into the solution, and stirring for 1-6 hours at 50-70 ℃; then crystallizing the solution; (2) after crystallization is finished, filtering and drying the crystallized product, uniformly mixing the crystallized product with a peptizing agent and an extrusion aid, kneading and molding, and drying and roasting to obtain a composite carrier;
(3) loading VIII group noble metal on the carrier obtained in the step (2), and drying and roasting to obtain a catalyst;
in the step (1), the molar ratio of the template agent, the organic acid, the inorganic acid and the tertiary butanol is (0.01-1): 1-20): 100; the mass fraction of the tertiary butanol in the tertiary butanol-water binary solvent is 3.9-93.6%; the mass fraction of the aluminum isopropoxide in the solution is 5-30%; the mass fraction of the Silicate-1 in the solution is 0.001-0.1%; the mass fraction of the HZSM-5 in the solution is 0.001-0.1%.
2. The catalyst of claim 1, wherein: the VIII group noble metal is one or more of Pt and Pd.
3. The catalyst of claim 1, wherein: the catalyst contains inorganic refractory oxide, and the inorganic refractory oxide is one or more of alumina, silica, titanium oxide, magnesium oxide and zirconium oxide.
4. A process for the preparation of a catalyst according to any one of claims 1 to 3, characterized in that: the method comprises the following steps: the in-situ synthesis method is adopted to prepare the catalyst containing Silicate-1, HZSM-5 and P2O5A composite carrier of an inorganic refractory oxide; then loading VIII group noble metal on a carrier to prepare a catalyst; the method specifically comprises the following steps:
(1) adding a template agent, an organic acid and an inorganic acid into a tert-butyl alcohol-water binary solvent according to a certain proportion, and adjusting the pH value of the solution to 1-3; adding aluminum isopropoxide, Silicate-1 and HZSM-5 into the solution, and stirring for 1-6 hours at 50-70 ℃; then crystallizing the solution;
(2) after crystallization is finished, filtering and drying the crystallized product, uniformly mixing the crystallized product with a peptizing agent and an extrusion aid, kneading and molding, and drying and roasting to obtain a composite carrier;
(3) loading VIII group noble metal on the carrier obtained in the step (2), and drying and roasting to obtain a catalyst;
wherein in the step (1), the molar ratio of the template agent to the organic acid to the inorganic acid to the tertiary butanol is (0.01-1): 1-20): 100; the mass fraction of the tertiary butanol in the tertiary butanol-water binary solvent is 3.9-93.6%; the mass fraction of the aluminum isopropoxide in the solution is 5-30%; the mass fraction of the Silicate-1 in the solution is 0.001-0.1%; the mass fraction of the HZSM-5 in the solution is 0.001-0.1%.
5. The method of claim 4, wherein: in the step (1), the template is a mesoporous template; the organic acid is one or more of citric acid and tartaric acid; the inorganic acid is one or more of phosphoric acid and boric acid.
6. The method of claim 4, wherein: in the step (1), the crystallization temperature is 80-200 ℃; the crystallization time is 8-48 hours.
7. The method of claim 4, wherein: in the step (2), the peptizing agent is nitric acid, hydrochloric acid, acetic acid or citric acid.
8. The method of claim 4, wherein: in the step (2), the drying temperature is 80-200 ℃, and the drying time is 6-48 hours; the roasting temperature is 300-900 ℃, and the roasting time is 2-24 hours.
9. The method of claim 4, wherein: in the step (3), the loading mode of the VIII group noble metal is an impregnation method; the drying temperature is 80-200 ℃, and the drying time is 6-48 hours; the roasting temperature is 300-800 ℃, and the roasting time is 2-24 hours.
10. The use of the catalyst of any one of claims 1 to 3 for the purification of t-butanol, characterized in that: the reaction conditions are as follows: adopting a fixed bed reactor, wherein the volume ratio of the tert-butyl alcohol raw material to the hydrogen is (10-100): 1; the feeding volume airspeed is 0.5-3.0 h-1(ii) a The reaction temperature is 150-300 ℃; the reaction pressure is 0.5-5 MPa.
11. Use according to claim 10, characterized in that: before the catalyst is used, reduction treatment needs to be carried out in advance in a hydrogen atmosphere, and the reduction temperature is 200-600 ℃; the reduction time is 2-12 hours.
CN201711119008.XA 2017-11-14 2017-11-14 Tert-butyl alcohol refining catalyst and preparation method and application thereof Active CN109772439B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711119008.XA CN109772439B (en) 2017-11-14 2017-11-14 Tert-butyl alcohol refining catalyst and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711119008.XA CN109772439B (en) 2017-11-14 2017-11-14 Tert-butyl alcohol refining catalyst and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN109772439A CN109772439A (en) 2019-05-21
CN109772439B true CN109772439B (en) 2022-02-08

Family

ID=66494002

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711119008.XA Active CN109772439B (en) 2017-11-14 2017-11-14 Tert-butyl alcohol refining catalyst and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN109772439B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111318301A (en) * 2018-12-13 2020-06-23 中国石油化工股份有限公司 Tert-butyl alcohol refining catalyst and preparation method and application thereof
CN112723995B (en) * 2019-10-28 2023-01-10 中国石油化工股份有限公司 Tert-butyl alcohol refining catalyst and preparation method and application thereof
CN112717994A (en) * 2019-10-28 2021-04-30 中国石油化工股份有限公司 Refined catalyst and preparation method and application thereof
CN112717922B (en) * 2019-10-28 2023-01-10 中国石油化工股份有限公司 Tert-butyl alcohol pretreatment catalyst and preparation method and application thereof
CN114436774B (en) * 2020-10-30 2024-06-11 中国石油化工股份有限公司 Purification method and purification system for alcohol solvent
CN112573998B (en) * 2020-12-07 2023-01-13 万华化学集团股份有限公司 Refining method of tertiary butanol

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1511815A (en) * 2002-12-31 2004-07-14 中国石化集团齐鲁石油化工公司 Process for preparing tertiary butanol
DE102006054519A1 (en) * 2006-11-20 2008-05-21 Evonik Degussa Gmbh Process for the preparation of fatty acid alkyl esters and acrolein from triglycerides
FR2994183B1 (en) * 2012-08-06 2015-07-31 Roquette Freres PROCESS FOR PREPARING DIALKYLOXYDIANHYDROHEXITOLS BY ETHERIFYING DIANHYDROHEXITOLS WITH LIGHT ALCOHOL IN THE PRESENCE OF AN ACIDIC CATALYST
CN105294385B (en) * 2015-12-01 2017-09-22 中国科学院大连化学物理研究所 A kind of method that decalin base prepares the t-butyl naphthalin of 2 methyl 6
CN108460515A (en) * 2018-01-16 2018-08-28 中国海洋石油集团有限公司 A kind of electric immersible pump well unit failure risk prediction technique
CN112785091A (en) * 2021-03-04 2021-05-11 湖北工业大学 Method for performing fault prediction and health management on oil field electric submersible pump

Also Published As

Publication number Publication date
CN109772439A (en) 2019-05-21

Similar Documents

Publication Publication Date Title
CN109772439B (en) Tert-butyl alcohol refining catalyst and preparation method and application thereof
CN107735392B (en) Method for preparing cucumis melo aldehyde
EP2981515B1 (en) Process for the preparation of glycols
JP4335445B2 (en) Method for producing molded article using metal oxide sol, molded article, and use thereof in producing alkene oxide
JP6629388B2 (en) Copper-based catalyst precursor, method for producing the same, and hydrogenation method
CN107721821B (en) Method for preparing 1, 3-propylene glycol
JP7050066B2 (en) Methods and systems for producing glycolic acid and / or glycolates
CN109890782A (en) Produce the single-stage process of butadiene
CN106040282A (en) SO 3H-SBA-15 molecular sieve catalyst for catalyzing synthesis of tert-butyl carboxylate from isobutene and carboxylic acid, and preparation method and application thereof
CN113480417B (en) Method for synthesizing isooctyl aldehyde by catalyzing n-butyl aldehyde with solid catalyst in one step
CN110325497B (en) Process for preparing unsaturated alcohols
CN105797719A (en) Load type duplex metal/multi-metal catalyst for hydrogenation synthesis of metanilic acid from m-Nitrobenzenesulfonic acid and preparation method and application
CN103373915B (en) A kind of catalytic oxidation prepares the method for di-carboxylic acid
CN111318301A (en) Tert-butyl alcohol refining catalyst and preparation method and application thereof
CN111097495A (en) Tert-butyl alcohol refining catalyst and preparation method thereof
CN101774944B (en) Acetonitrile production process
CN111097509A (en) Catalyst for refining tertiary butanol and preparation method thereof
JP3862883B2 (en) Nuclear hydrogenation process for aromatic epoxy compounds
TWI628000B (en) Catalyst and method for hydrogenation of 1,3-cyclobutanediketone compound
CN112723995B (en) Tert-butyl alcohol refining catalyst and preparation method and application thereof
CN112717922B (en) Tert-butyl alcohol pretreatment catalyst and preparation method and application thereof
CN107285994B (en) Method for synthesizing cinnamyl alcohol by selective hydrogenation of cinnamyl aldehyde
CN108774106B (en) Method for extracting sec-octanone from crude sec-octanol and hydrogenating to prepare sec-octanol and catalyst thereof
JP6269026B2 (en) Production of diisobutyl carbinol by hydrogenation of diisobutyl ketone
KR20120035760A (en) PALLADIUM-ALUMINA COMPLEX CATALYST FOR PRODUCTION OF γ-BUTYROLACTONE BY HYDROGENATION OF SUCCINIC ACID, PREPARATION METHOD THEREOF AND PRODUCTION METHOD FOR γ-BUTYROLACTONE BY HYDROGENATION OF SUCCINIC ACID USING SAID CATALYST

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20231012

Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen

Patentee after: CHINA PETROLEUM & CHEMICAL Corp.

Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd.

Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen

Patentee before: CHINA PETROLEUM & CHEMICAL Corp.

Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp.

TR01 Transfer of patent right